Synthetic lubricants



United States Patent SYNTHETIC LUBRICANTS Charles F. Feasley, Woodbury, William E. Garwood, Haddonfield, Alexander N. Sachanen, Woodbury, and Francis M. Seger, Pitman, N. J., assigrcors to Soccny Mobil Oil Company, Inc., a corporation of New York No Drawing. Original application August 30, 1951, Se-

rial No. 244,482. Divided and this application July 29, 1955, Serial No. 527,178

6 Claims. (Cl. 260-290) This invention has to do with the condensation of normal alpha mono-olefins, heterocyclic compounds and or ganic peroxides, and particularly has to do with the new and useful compositions obtained by said condensation.

This application is a division of our application Serial No. 244,482, filed August 30, 1951, which issued as Pat- As is also well known to those familiar with the art,

polymerization reactions of the type referred to hereinbefore may be conducted at relatively high temperatures and pressures, in the presence of substances or of mixtures of substances that promote the polymerization reaction. These substances are referred to as polymerization catalysts.

Several substances have been proposed as polymerization catalysts, and among the most widely used are phosphoric acid, sulfuric acid, hydrogen fluoride, aluminum chloride, boron trifluoride and solid alumina-silica absorbents. In polymerization processes involving the use of these substances as catalysts, olefinic hydrocarbons are polymerized into polymeric olefinic hydrocarbons, the mo lecular weight of which, depending upon the conditions of polymerization, may vary within very broad limits from dimers to polymers containing many thousands of carbon atoms. These products may be used as fuels, lubricants, plastics, etc., depending upon their molecular weights. 1

It is also well known to those familiar with the art, that ethylene and conjugated diolefinic hydrocarbons,

such as butadiene, are readily polymerized in the presence of peroxides or oxygen. This has been embodied in numerous processes which are of considerable commercial importance in the production of high molecular weight plastics and elastomers, In contrast to the polymers formed in the polymerization of ethylene or of conjugated diolefinic hydrocarbons in the presence of acidic polymerization catalysts, the products obtained when peroxides or oxygen are utilized as polymerization catalysts are predominantly high molecular weight polymers.

We have discovered that normal, alpha mono-oleiins condense, simultaneously, with certain heterocyclic compounds and with organic peroxides, under conditions hereinafter defined, with the formation of desirable viscous oils. The oils so formed arecharacterized by relatively high specific gravity, high viscosity index and low pour point. Certain of the oils exhibit an unusually high degree of stability to oxidation.

REACT ANTS As indicated above, the mono-olefin reactants of this invention are normal or straight chain alpha mono-olefins. These olefins contain from about 8 to 18 carbon atoms. Such mono-olefins are normally liquid at temperatures of the order of 20-25 C. Illustrative of such mono-olefins are the following: n-octene-l, n-decene-l, n-dodecene-1, n-hexadecene-l, n-octadecene-l, and the like. Preferred, however, of such olefins are those having from 8 to 12 carbon atoms, with n-decene-l repre-' senting a particularly desirable olefin. It will be clear from the foregoing examples that an alpha olefin may also be referredto as a l-olefin.

Not only may the mono-olefins of the aforesaid character be used individually in this invention, but they may also be used in admixture with each other. In addition, olefin mixtures containing a substantial proportion of such mono-olefins may be used. Preferred of such mix tures are those containing a major proportion of a l-olefin or of l-olefins. Representative of such mixtures are those obtained by the cracking of paraffin waxes and other parafiin products, and those obtained from the Fischer- Tropsch and related processes.

These hydrocarbon mixtures may contain, in addition to the l-olefin or l-olefins, such materials as: other olefins, paraffins, naphthenes and aromatics.

in general, any organic peroxide is suitable for our purpose. By organic peroxide we mean those organic compounds which contain an -O--O- linkage. In this connection, it must be clearly understood that when we speak of organic peroxides herein and in the claims we have reference to organic hydroperoxides as well as simple organic peroxides. The organic peroxides utilizable in the process of the present invention may be aliphatic peroxides, aromatic peroxides, heterocyclic peroxides and alicyclic peroxides. Diethyl peroxide, tertiary butyl hydroperoxide, benzoyl peroxide, dimeth'ylthienyl peroxide, cyclohexyl peroxide, and lauroyl peroxide may be mentioned by way of non-limiting examples of organic peroxides suitable for the process of our invention. In general, we prefer to use those organic peroxides containing the radical o R C O- wherein R is an aliphatic or aromatic radical, such as acetyl peroxide, and of these, we especially prefer to use those containing a benzene ring, such as benzoyl peroxide. The organic peroxides may be derived from any suitable source as is well understood and, advantageously, may be formed in situ, thereby obviating the necessity of using the relatively expensive commercial organic peroxides. Such a modification must be considered to be within the scope of the present invention, although the use of individual organic peroxides is preferred.

The formation of the organic peroxides in situ may be accomplished in a number of ways. For example, they may be formed in accordance with the procedure of Price and Krebs (Organic Syntheses, 23, 6S (1943)), or by contacting oxygen or air, preferably moist air, with a suitable organic compound such as a hydrocarbon, or an ether, which reacts therewith to form the desired organic peroxide. Ethyl benzene, cyclohexene, and tetralin which readily form peroxides on oxidation, may be mentioned by way of non-limiting examples of organic compounds utilizable for forming the organic peroxides in situ,

In general, and in accordance with our invention, the amounts of organic peroxide to be used are relatively large. the prior artwhich involve conjugated diolefinic hydrocarbons or ethylene wherein organic peroxides function as catalysts in the widely accepted sense of the term, we have found that in our process, the decomposition products of organic peroxides combine with the normal alpha mono-olefins and heterocyclic compounds.

In contrast to the polymerization reactions of Accordingly,

the yields and nature of the products obtained in the process of the present invention depend upon the amount of and reflect the type of organic peroxides employed. For instance, when benzoyl peroxide is reacted with a normal, alpha mono-olefin and an aromatic hydrocarbon in accordance with our process, products containing structural fragments of the benzoyl peroxide are formed. This is demonstrated by saponification values for the products. Viewed in this light, our process is one involving both polymerization and the broader and more comprehensive reaction-condensation.

Heterocyclic compounds, by definition, have a closed chain or ring which contains, in addition to carbon, at least one atom of nitrogen, oxygen, sulfur or the like. The heterocyclic compounds used herein are those which are not readily oxidized or which are resistant to oxidation, as shown by a simple test procedure. Equal quantities, cc., of decene-l and of a heterocyclic compound are mixed in a 25 cc. graduate, and the resulting mixture is allowed to come to equilibrium such that its temperature is the same as the surroundings. One gram of benzoyl peroxide is then added to the mixture, which is agitated by shaking the graduate. The maximum temperature deviation during a ten minute period is noted. An increase in temperature of more than 1 C. (using a temperature measuring means accurate to 0.2 C.) is interpreted as an indication that the heterocyclic compound is easily oxidized and will be inoperative in the present process. In other words, heterocyclic compounds showing a temperature rise of 1 C. or more in this test apparently react so rapidly with the peroxide that there is little or no interreaction of the heterocyclic compound, normal alpha mono-olefin and peroxide.

Illustrative of the heterocyclic compounds contemplated herein and of those which are too readily oxidized to be used are several typical examples given below. In the case of heterocyclic compounds containing oxygen quired to dissolve the peroxide, Clearly, no oxidation occurred. Other heterocyclics of this type are: furan, pyran, benzofuran, thiapyran, benzothiophene and thianthrene.

With nitrogen-containing heterocyclic compounds, the

valence requirements of the nitrogen (valence of 3) may or may not be satisfied by the ring. Only those compounds in which the valence requirements are met by the ring are satisfactor Pyridine,'alpha-picoline and quinoline are examples of operative heterocyclic nitrogen com pounds, all having a maximum temperature deviation in the foregoing test of l C. In contrast, pyrrole and morpholine, which have a hydrogen atom attached to a ring nitrogen atom, have temperature deviations of at least 10 C. and are inoperative herein. Nicotine is characterized by one ring nitrogen atom attached to a methyl group, and exhibits a deviation of +17 C. It

Mixed heterocyclic compounds meeting the aforesaid test requirement are also considered satisfactory, typical of which are oxazole, thiazole and benzothiazole. Inoperable mixed heterocyclic compounds include morpholine, phenothiazine and Z-mercaptobenzothiazole.

Heterocyclic compounds containing relatively inert subrepresented by chlorine. For example, 2-chlorothiophene has a maximum temperature deviation of 1 C. in the foregoing test. In contrast, a mercapto group is relatively reactive and should be avoided. By way of illustration, 3-thiophene thiol has a maximum temperature deviation of +2 C. As indicated above, 2-mercaptobenzothiazole is also unsatisfactory. Alkyl substituents attached to a ring nitrogen atom such as a methyl group attached to a ring nitrogen atom are also to be avoided, as demonstrated by nicotine which contains an N-methyl grouping.

In accordance with the process of the present invention and depending upon the conditions of operation and the nature of the mono-olefinic hydrocarbon reactants, various condensation products, from comparatively low-boiling to high-boiling fractions, can be synthesized. Thus, in our process, it is possible to produce fractions boiling within the range of those of lubricating oils, i. e., above 700 F. These products are of particular interest and importance. For example, synthetic lubricating oils obtained in accordance with our process generally have high specific gravities, low pour points and good viscosity characteristics. In contrast to synthetic lubricating oils obtained in the processes of the prior art involving solely the polymerization of olefinic hydrocarbons, those of the present invention contain not only paraffinic chains but also contain heterocyclic nuclei and other structural elements depending upon the organic peroxide and heterocyclic material used. Further, the synthetic lubricating oils synthesized by the alkylation of aromatics with ole finic hydrocarbons or chlorinated alkanes will differ materially from those of our invention due to the very nature of the reactions involved. Thus, as is well known,

catalysts which induce a series of side reactions, such as On the contrary, in our process, the reaction is aflfected under conditions whereby side reactions, if any, are kept to a minimum, and the temperature conditions are comparatively mild. Accordingly, the utilization of our process for the manufacture of synthetic lubricating oils must be considered a preferred, but nevertheless non-limiting embodiment of our invention.

CONDENSATION CONDITIONS In carrying out condensation of the aforesaid reactants, temperatures varying between about 50 C. and about 200 C. are usually used, depending primarily, however, upon the kind of organic peroxide employed. In general, temperatures of the order of C. to

temperatures.

When benzoyl peroxide is used, the temperature may vary between about 50 C. and about C. and, preferably, between about 80" C. and 100 C. On the other hand, when hydroperoxides are used, the temperature may vary between about 100 C. and about 200C and is preferably of the order of C. The pressure to be employed depends upon the temperature used and, ordinarily, a pressure sufficient to maintain the reactants in substantially a liquid phase at the temperature employed is adequate.

The time of reaction depends upon the temperature, the nature of the reactants employed, the quantity of reactants, and to a certain extent upon the pressure. In general, the higher the temperature employed the shorter the reaction time required, the criterion used being the time required at a given reaction temperature to eifect condensation and, more specifically, to assure substantial- This is evidenced by the peroxide frag- When the peroxide is consumed, no further condensation takes place and oil products are obtained. Thus the time of reaction can be designated as one suflic ient to effect condensation? Generally, satisfactory results are obtained when the time period is between about five and about fifteen hours, with the reactants and quantities of reactants such as shown in the illustrative examples described hereinafter.

avian-s se for. oxidation to the peroxide, with the simultaneous or subsequent reaction to bring about the condensation of the mono-olefinic hydrocarbon reactant and the unreacted heterocyclie reactant with. that portion of the hetero As indicated above, the amounts of organic peroxides 5 cyclic reactant which has been converted toperoxide. and heterocyclic compounds employed determine, to a' The process may be carried out as a batch, continuous great degree, the yield and quality of the products. Reor semi-continuous type of operation. Particularly when action may be obtained using between about 0.01 and the process is carried out on acommercial scale, economic about 0.5 molar proportionof. a peroxide, with between considerations make it preferable to operate in a conabout 0.01 to about 6.0 molar proportion of aheterocyclic l0 tinuous manner. For eflicient operation, whether the compound, with one molar proportion of a normal, alpha process is carried out on a batch or continuous basis, it is mono-olefin. Preferably, however, we employ organic fess'ential that the mono-olefinic hydrocarbon reactant be peroxides in amounts varying between about 0.05 and intimately contacted with the organic peroxide and with about 0.1 molar proportion, with between about 0.1 and the heterocyclic compound. .This may be efiected in about 2.0 molar proportion of heterocyclic compound, several ways and in apparatus which is well known in the Y with one molar proportion of mo'rio-olefiu. in all cases, art. the quantity of peroxide usedis a-reactive quantity as dis- EXAMPLES lihguished from merely a Catalytic quantity, for the P The following detailed examples are for the purpose oxide reactant enters into the condensation and fragments f illustrating modes of carrying out the process f thereof form components of the condensation products. invention It is to be understood however, that the i This is in sharp contrast with polymerization reactionsof vemioh is not to be considered as li i d to e ifi the Prior art Which involve whlugated diolefihs of l actants or to the specific conditions of operation setforth wherein Organic peroxides fuhcthih as Catalysts herein. As will be apparent to those skilled in the art, the Widely accepted Sense 0ftheteFmata1Y$t5- a wide variety of other mono-olefinic hydrocarbon rehl Carrying out the Process of the Preseht ihvehhoh the actants, heterocyclic reactants, and organic peroxides may organic peroxide is added to the mono-olefin and heterobe s Cyclic COmPOImd, Preferably two e poftiohs at The general procedure followed in the making of the intervals of a few hoursf f the Organ: P P P example runs was substantially the same in all cases. The ids y be added n some instances a Single d olefin reactant and the heterocyclic reactant were stirred although excessive heat of reactieh may he developedtogether and heated while the peroxide was added at in- When the organic peroxide is formed in situ, a mixture tervals A tempfiramre f 3 to C and time f of the mono'olefih and hetel'ocyehc compound. and an about nine to ten hours were found sufiicieut to cause the efgahie Compound Which forms an Organic Peroxlde when reaction to go to substantial completion. The crude resubjected to Oxidation, in amounts at least about 5%, action product freed of molecular eight com- Preferably a least about 20%, based QHIhe Weight 35 ponents and the desirable condensation products were ohthe mono-olefinic hydrocarbon reactant, is contacted with tamed as Oily residues s f the peroxide fragments yg n for p under the Conditions of were eliminated as benzoic acid and then removed by action to produce the organic peroxide in S u at the alkali washing or by distillation. This can be considered Same time that the condensatiohreactlon P The to be an operating loss. The unreacted olefins, recovered cchtact with Oxygen may be effected by o at Pi the by distillation, were suitable for recycling. The oily prodmiXhlTe in air, bubbling of the thmugh the mlxmre, uct was tested without any other treatment, refining and i I r without additives.

n nother embodiment Of this modlficatwn, 3 Orgamc To distinguish the condensation products from the disw r is Peroxidized to a desired degree before the tillate fractions thereof, the oily residues are identified addition. of the olefinic. hydrocafbonl reactant and the 45 as residual oils. The latter term identifies the oils from heterbcyclic reactant- Yet another modification is to use which unreacted materials, by-products (as any benzoic the mohh-hlefihie hydfocafbonieacmntper 5 for mid? acid) and products of intermediate boiling range have tion to the peroxide, with simultaneous or subsequent rebeen Separated. action to bring about the Condensation 0f t B w All of the tests and analyses to which the residual oils m fi hydfoeafbhh reactant and h hetel'heyehc 5 in Table I were subjected are well known standard tests. reactant, with that Portion of the moho-hlefihic yd In this connection, it will be noted that the designation carbon which has been converted to peroxide. Still an- N. N. refers to the neutralization number, which is a other modification is to use the heterocyclic reactant per measure of the acidity of the oil.

Table I RunNo. 1 2 3 4 5 6 Mono-olefin; n-Decene-1. n-Decene-L. n-Decene-L. n-Decene-L. n-Decene-l.

Parts byWe1ght... 420 t 420 7 0 1 20. naiifiiir'aiffiffffii. m gra nes? Itiorpholinc.

1H9. 7 Parts by Weight. 268. Molar Proportion Perox e Benzoyl.

Parts by Weight 5 Temperature, C... Time, Hrs;

Residual Oil:

Parts by Weight Percent Yield K. V. O0 F., 0;. K. V. 210 F., Cs. V. I. Pout Point, F Br. Addn. No

Speeific Gravity N. N Sa o iflcatlon No B or; Pei-cents" Nitrogen, Perceut....-

Footnotes at end of table.

Table l-Contmued Run No 7 8 9 10 11 Mono-olefin n-Decene-l n-Decene-l n-Decene-l n-Hexadecene-l n-lHexadecene- Parts by Weight 224.

Molar Proportion. 3 1.0. Heterocyclic 'Ihmphene.

Parts by Weight 35 84.

Molar Proportion 1.Q. Peroxide Di-t-butyl.

Parts by Weight 15.

Molar Proportion. 0.1. Temperature, C. 140. Time, Hrs t 14 8. Residual 011:

Parts by Weight 81 99.

Percent Yield 31.

K. V. 100 F Cs. 111.5.

K V 210 F Os 16.59.

Pour Point, 45.

Br. Addn. No 16.1.

Specific Gravity 0.8519.

Saponification No Sulfur, Percent 0.74.

Nitrogen, Percent 1 Percent hydrogen, 12.67; percent carbon, 81.88. 3 Molecular weight=407.

In Table I above, runs 1-4 illustrate excellent synthetic oils obtained with the present invention. All of the oils of runs 14 have high viscosity indices (91-112) and have desirably low pour points. Run 1 is illustrative of an oil obtained with a suitable sulfur-containing heterocyclic compound, thiophene, and run 2 is illustrative of an oil obtained with a suitable oxygen-containing heterocyclic compound, dioxane. Pyridine and alphapicoline in runs 3 and 4, respectively, illustrate operative nitrogen-containing heterocyclic compounds. The low yield obtained in run 4 with alpha-picoline is due to a high ratio of the heterocyclic compound to olefin; with lower ratios, increasing yields of desirable oils may be obtained.

Run 5 is illustrative of the low degree of reaction or condensation obtained with nicotine, which is too readily oxidized to be used herein.

Run 6, in which morpholine is used, is also illustrative of too readily oxidizable nitrogen-containing heterocyclic compounds. The morpholine product was made from a reaction mixture containing a relatively small amount of morpholine. Low viscosity index and high nitrogen content indicate little reaction of the olefin and much side reaction of morpholine with peroxide.

Mercaptooenzothiazole, in run 7, is another unsatisfactory-heterocyclic compound, as shown by the very low viscosity index, 2.6, of the oil product. The high sulfur content of the oil product is indicative of relatively little reaction of olefin, heterocyclic compound and peroxide.

Run 8 shows a mixed heterocyclic compound, phenothiazine, which is too readily oxidized to be of value in this invention. Similarly, run 9 shows a substituted heterocyclic having a highly reactive substituent group, mercapto or thiol.

Runs 10 and ll are illustrative of oils obtained from a relatively long chain olefin, n-hexadecene-l. It will be noted that these oils have desirably high viscosity indices, 124.5 and 137.3, respectively.

As will be evident from the data presented above in Table I, the condensation products of this invention are highly desirable lubricants per se. They are also of considerable value as blending agents for other lubricating oils. They impart desirable viscosity index (V. l.) and pour point characteristics to the oils in combination therewith, for, as indicated above, they have advantageous viscosity and pour point properties. In short, the synthetic oils find utility in upgrading other lubricants. Typical oils with which the synthetic oils may be blended are mineral oils such as are normally used in internal combustion and turbine engines. When so blended, the

synthetic oils may comprise the major proportion of the final blended oil, or may even comprise a minor proportion thereof.

One or more of the individual properties of the synthetic lubricants of this invention may be further improved by incorporating therewith a small but effective amount, of an addition agent such as an antioxidant, a detergent, an extreme pressure agent, a foam suppressor, a viscosity index (V. I.) ,improver, etc. Antioxidants for viscous oils are well known in the art, and generally contain sulfur, nitrogen, oxygen. and/or phosphorus. Representative of such antioxidants is a phosphorus-andsulfur containing reaction product of pinene and P285. Typical detergents which may be so used are metal salts. of alkyl-substituted aromatic sulfonie or carboxylic acids, as illustrated by diwax benzene barium sulfonate and barium phenate, barium salt of a wax-substituted phenol carboxylic acid. Extreme pressure agents are well known; illustrating such materials are'numerous chlorine and/or sulfur containing compositions, one such material being a chlor-naphtha xanthate. Silicones, such as dimethyl silicone, may be used to illustrate foam suppressing compositions. Viscosity index improving agents which may be used are typified by polypropylenes, polyisobutylenes, polyacrylate esters, and the like.

contemplated also as within the scope of this invention is a method of lubricating relatively moving surfaces by maintaining therebetween a film consisting of any of the aforesaid oils. 1

It is to be understood that the foregoing description and representative examples are non-limiting and serve to illustrate the invention, which is to be broadly construed in the light of the language of the appended claims.

We claim:

1. An oil of lubricating viscosity characterized by relatively high specific gravity, high viscosity index and low pour point and obtained by: condensing at a temperature between about C. and about C. for a period of time between about 5 hours and about 10 hours, one molar proportion of a normal alpha-mono olefin having from 8 to 18 carbon atoms per molecule, between about 0.01 and about 0.5 molar proportion of an organic peroxide selected from the group consisting of tertiary butyl peroxide and benzoyl peroxide, and from about 1 to 6 molar proportions of a heterocyclic compound selected from the group consisting of pyridine and alpha picoline, and separating said oil from the 7 reaction product thus formed.

2. The process for preparing an oil of lubricating viscosity characterized by relatively high specific gravity,

high viscosity index and low pour point which comprises: heating at a temperature between about 80 C. and about 140 C. for a period of time between about 5 hours and about 10 hours, one molar proportion of a normal alpha-mono olefin having from 8 to 18 carbon atoms per molecule, between about 0.01 and about 0.5 molar proportion of an organic peroxide selected from the group consisting of tertiary butyl peroxide and benzoyl peroxide, and from about 1 to 6 molar proportions of a heterocyclic compound selected from the group consisting of pyridine and alpha picoline, and separating said oil from the reaction product thus formed.

3. The process for preparing oil of lubricating viscosity characterized by relatively high specific gravity, high viscosity index and low pour point, which comprises: heating at a temperature of about 85 C. for about 9 hours, one molar proportion of n-decene-l with six molar proportions of alpha picoline and with 0.1 molar proportion of benzoyl peroxide and separating said oil from the reaction mixture thus formed.

4. The process for preparing oil of lubricating viscosity characterized by relatively high specific gravity, high viscosity index and low pour point, which com- 10 prises: heating at a temperature of about 85 C. for about nine hours, one molar proportion of n-decene-l with one molar proportion of pyridine and with 0.1 molar proportion of benzoyl peroxide, and separating said oil from the reaction product thus formed.

5. An oil of lubricating viscosity characterized by relatively high specific gravity, high viscosity index and low pour point obtained by: condensing at a temperature of about 85 C., for about nine hours, one molar proportion of n-decene-l with one molar proportion of pyridine and with 0.1 molar proportion of benzoyl peroxide, and separating said oil from the reaction product thus formed.

6. An oil of lubricating viscosity characterized by relatively high specific gravity, high viscosity index and low pour point and obtained by: condensing, at a temperature of about 85 C. for about nine hours, one molar proportion of n-decene-l with six molar proportions of alpha-picoline and with 0.1 molar proportion of benzoyl peroxide, and separating said oil from the reaction product thus formed.

No references cited. 

1. AN OIL OF LUBRICATING VISCOSITY CHARACTERIZED BY RELATIVELY HIGH SPECIFIC GRAVITY, HIGH VISCOSITY INDEX AND LOW POUR POINT AND OBTAINED BY: CONDENSING AT A TEMPERATURE BETWEEN ABOUT 80* C. AND ABOUT 140* C. FOR A PERIOD OF TIME BETWEEN ABOUT 5 HOURS AND ABOUT 10 HOURS, ONE MOLAR PROPORTION OF A NORMAL ALPHA-MONO OLEFIN HAVING FROM 8 TO 18 CARBON ATOMS PER MOLECULE, BETWEEN ABOUT 0.01 AND ABOUT 0.5 MOLAR PROPORTION OF AN ORGANIC PEROXIDE SELECTED FROM THE GROUP CONSISTING OF TERTIARY BUTYL PEROXIDE AND BENZOYL PEROXIDE, AND FROM ABOUT 1 TO 6 MOLAR PROPORTIONS OF A HETEROCYCLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF PYRIDINE AND ALPHA PICOLINE, AND SEPARATING SAID OIL FROM THE REACTION PRODUCT THUS FORMED. 